Radical polymerization initiator and method for producing polymers

ABSTRACT

The present invention involves a radical polymerization initiator comprising an organotellurium compound represented by a formula (1), wherein R 1  represents an alkyl group or the like, each of R 2  and R 3  independently represents a hydrogen atom or the like, and each of R 4 , R 5 , and R 6  independently represents a hydrogen atom or the like. 
     The present invention provides: a radical polymerization initiator that is useful for producing a polymer that includes a double bond at the molecular terminal; and a method for producing a polymer that utilizes the radical polymerization initiator.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional of U.S. application Ser. No. 15/038,579 filed onMay 23, 2016, which is a 371 of PCT/JP2014/081334 filed on Nov. 27, 2014which claims foreign priority to Japanese Application No. 2013-245352filed on Nov. 27, 2013, the entire contents of which is incorporatedherein by reference.

TECHNICAL FIELD

The present invention relates to a radical polymerization initiator thatis useful for producing a polymer that includes a double bond at themolecular terminal, and a method for producing a polymer that utilizesthe radical polymerization initiator.

BACKGROUND ART

A polymer that includes a double bond at the molecular terminal is usedas a macromonomer when producing a polymer that has a branched structure(e.g., graft polymer or star-shaped polymer).

For example, Patent Literature 1 discloses a method for producing apolymer having a branched structure wherein a macromonomer ispolymerized, the macromonomer including a group that includes apolymerizable carbon-carbon double bond at the molecular terminal.Patent Literature 1 discloses a method for producing a macromonomerwherein a vinyl-based monomer is polymerized using an atom transferradical polymerization method that utilizes a polymerization initiator(e.g., organic halide) and a catalyst (e.g., transition metal complex)to obtain a vinyl-based polymer that includes a terminal halogen group,and the terminal halogen group is substituted with a compound thatincludes a double bond, for example.

When using the method disclosed in Patent Literature 1 wherein afunctional group (e.g., halogen group) situated at the molecularterminal is substituted with a group that includes a carbon-carbondouble bond, it is necessary to effect a functional group substitutionreaction. Therefore, a method that introduces a carbon-carbon doublebond into the polymerization-initiation terminal using a polymerizationinitiator that includes a carbon-carbon double bond has been studied inorder to more easily obtain a macromonomer. Examples of such a methodinclude an atom transfer radical polymerization method that utilizes anallyl halide as a polymerization initiator (see Non-Patent Literature1). However, the type of vinyl-based monomer that can be applied to theatom transfer radical polymerization method that utilizes an allylhalide as a polymerization initiator is limited. Moreover, it may bedifficult to control the polymerization reaction, or the polymerizationreaction may not proceed depending on the type of vinyl-based monomer.In view of the above situation, a radical polymerization initiator thatincludes a carbon-carbon double bond, and can be applied to a widevariety of radically polymerizable monomers (e.g., vinyl-based monomer)to implement a controlled polymerization reaction, has been stronglydesired.

However, since a radical polymerization initiator has reactivity with acarbon-carbon double bond, a radical polymerization initiator normallydoes not exhibit sufficient polymerization activity when a carbon-carbondouble bond is introduced into the molecule of the radicalpolymerization initiator. Specifically, a radical polymerizationinitiator that includes a carbon-carbon double bond and has the desiredproperties has not yet been obtained.

An organotellurium compound is known as a radical polymerizationinitiator that makes it possible to subject a vinyl-based monomer or thelike to radical polymerization while controlling the molecular weightdistribution and the like (see Patent Literature 2 and 3) .

CITATION LIST Patent Literature

Patent Literature 1: JP-A-2007-254758 (US2006/0052563A)

Patent Literature 2: WO2004/014962 (US2006/0167199A)

Patent Literature 3: JP-A-2007-277533

Non-Patent Literature

Non-Patent Literature 1: Yoshiki Nakagawa and Krzysztof Matyjaszewski,“Synthesis of Well-Defined Allyl End-Functionalized Polystyrene by AtomTransfer Radical Polymerization with an Allyl Halide Initiator”, PolymerJournal, 1998, Vol. 30, No. 2, pp. 138-141

SUMMARY OF INVENTION Technical Problem

The invention was conceived in view of the above situation. An object ofthe invention is to provide a radical polymerization initiator that isuseful for producing a polymer that includes a double bond at themolecular terminal, and can be applied to a wide variety of radicallypolymerizable monomers to implement a controlled polymerizationreaction, and a method for producing a polymer that utilizes the radicalpolymerization initiator.

Solution to Problem

The inventors conducted extensive studies with regard to a radicalpolymerization initiator that is used for a living radicalpolymerization reaction in order to solve the above problem. As aresult, the inventors found that a wide variety of radicallypolymerizable monomers can be polymerized in a controlled manner, and apolymer that includes a double bond at the molecular terminal can beefficiently obtained by subjecting a radically polymerizable monomer toa living radical polymerization reaction in the presence of a radicalpolymerization initiator that includes an organotellurium compound thatincludes at least one non-aromatic carbon-carbon double bond at theβ-position. This finding has led to the completion of the invention.

Several aspects of the invention provide the following radicalpolymerization initiator (see (1)), method for producing a polymer (see(2) to (5)), and polymer (see (6)).

(1) A radical polymerization initiator including an organotelluriumcompound represented by the following formula (1),

wherein R¹ represents a group selected from an alkyl group, asubstituted or unsubstituted cycloalkyl group, a substituted orunsubstituted aryl group, and a substituted or unsubstitutedheteroaromatic ring group, each of R² and R³ independently represents anatom or a group selected from a hydrogen atom, an aliphatic hydrocarbongroup, a substituted or unsubstituted aryl group, a substituted orunsubstituted heteroaromatic ring group, a halogen atom, a carboxylgroup, a hydrocarbyloxycarbonyl group, a cyano group, and an amidegroup, and each of R⁴, R⁵, and R⁶ independently represents an atom or agroup selected from a hydrogen atom, an aliphatic hydrocarbon group, asubstituted or unsubstituted aryl group, a substituted or unsubstitutedheteroaromatic ring group, a halogen atom, a carboxyl group, ahydrocarbyloxycarbonyl group, a cyano group, an amide group, and a grouprepresented by the following formula (2), provided that two groupsselected from R² to R⁶ are optionally bonded to each other to form aring other than an aromatic ring,

wherein R⁷ represents a group selected from an alkyl group, asubstituted or unsubstituted cycloalkyl group, a substituted orunsubstituted aryl group, and a substituted or unsubstitutedheteroaromatic ring group, each of R⁸ and R⁹ independently represents anatom or a group selected from a hydrogen atom, an aliphatic hydrocarbongroup, a substituted or unsubstituted aryl group, a substituted orunsubstituted heteroaromatic ring group, a halogen atom, a carboxylgroup, a hydrocarbyloxycarbonyl group, a cyano group, and an amidegroup, and the wavy line represents that the group represented by theformula (2) is bonded to the carbon atom included in the formula (1)that forms the double bond.(2) A method for producing a polymer including subjecting a radicallypolymerizable monomer to radical polymerization in a state in which theradical polymerization initiator according to (1) is present in apolymerization system.(3) The method for producing a polymer according to (2), wherein theradically polymerizable monomer is subjected to radical polymerizationin a state in which an azo-based radical generator is further present inthe polymerization system.(4) The method for producing a polymer according to (2) or (3), whereinthe radically polymerizable monomer is subjected to radicalpolymerization in a state in which light is applied to thepolymerization system.(5) The method for producing a polymer according to any one of (2) to(4), wherein the radically polymerizable monomer is subjected to radicalpolymerization in a state in which a ditelluride compound represented bythe following formula (3) is further present in the polymerizationsystem,

R¹⁰Te-TeR¹¹   (3)

wherein each of le and R¹¹ independently represents a group selectedfrom an alkyl group, a substituted or unsubstituted cycloalkyl group, asubstituted or unsubstituted aryl group, and a substituted orunsubstituted heteroaromatic ring group.(6) A polymer obtained by the method for producing a polymer accordingto any one of (2) to (5).

Advantageous Effects of Invention

The aspects of the invention thus provide a radical polymerizationinitiator that is useful for producing a polymer that includes a doublebond at the molecular terminal, and can be applied to a wide variety ofradically polymerizable monomers to implement a controlledpolymerization reaction, and a method for producing a polymer thatutilizes the radical polymerization initiator.

Note that the expression “includes a double bond at the molecularterminal” used herein means that a group represented by(R⁵)(R⁶)C═C(R⁴)-C(R²)(R³)- that is derived from the organotelluriumcompound represented by the formula (1) forms one of the terminals ofthe polymer chain.

DESCRIPTION OF EMBODIMENTS

A radical polymerization initiator and a method for producing a polymeraccording to the exemplary embodiments of the invention are described indetail below.

1) Radical Polymerization Initiator

A radical polymerization initiator according to one embodiment of theinvention includes the organotellurium compound represented by theformula (1).

R¹ in the formula (1) represents a group selected from an alkyl group, asubstituted or unsubstituted cycloalkyl group, a substituted orunsubstituted aryl group, and a substituted or unsubstitutedheteroaromatic ring group. Among these, an alkyl group and a substitutedor unsubstituted aryl group are preferable as R¹.

Note that the expression “substituted or unsubstituted” used herein inconnection with a group or the like means that the group or the like isunsubstituted, or substituted with a substituent.

The number of carbon atoms of the alkyl group that may be represented byR¹ is not particularly limited, but is preferably 1 to 10, morepreferably 1 to 8, and still more preferably 1 to 5, from the viewpointof availability.

Examples of the alkyl group that may be represented by R¹ include alinear alkyl group such as a methyl group, an ethyl group, an n-propylgroup, an n-butyl group, an n-pentyl group, an n-hexyl group, ann-heptyl group, an n-octyl group, an n-nonyl group, and an n-decylgroup; and a branched alkyl group such as an isopropyl group, asec-butyl group, and a tert-butyl group.

The number of carbon atoms of the cycloalkyl group (that is substitutedor unsubstituted) that may be represented by R¹ is normally 3 to 10. Thenumber of carbon atoms of the cycloalkyl group is preferably 3 to 8, andmore preferably 5 or 6, from the viewpoint of availability.

Examples of the cycloalkyl group (that is substituted or unsubstituted)that may be represented by R¹ include a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, acyclooctyl group, and the like.

A substituent that may substitute the cycloalkyl group (that issubstituted or unsubstituted) that may be represented by R¹ is notparticularly limited as long as the substituent does not hinder thepolymerization reaction. Examples of the substituent include a halogenatom such as a fluorine atom, a chlorine atom, a bromine atom, and aniodine atom; a hydroxyl group; an alkyl group having 1 to 8 carbonatoms, such as a methyl group, an ethyl group, an n-propyl group, and anisopropyl group; an alkoxy group having 1 to 8 carbon atoms, such as amethoxy group and an ethoxy group; an amino group; a nitro group; acyano group; a group represented by —CORa (wherein Ra represents analkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethylgroup, an n-propyl group, and an isopropyl group; a cycloalkyl grouphaving 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclobutylgroup, and a cyclopentyl group; an aryl group having 6 to 10 carbonatoms, such as a phenyl group, a 1-naphthyl group, and a 2-naphthylgroup; an alkoxy group having 1 to 8 carbon atoms, such as a methoxygroup and an ethoxy group; a substituted or unsubstituted aryloxy grouphaving 6 to 10 carbon atoms, such as a phenoxy group and a2,4,6-trimethylphenyloxy group; and a haloalkyl group having 1 to 8carbon atoms, such as a trifluoromethyl group; and the like.

The number of carbon atoms of the aryl group (that is substituted orunsubstituted) that may be represented by R¹ is normally 6 to 20. Thenumber of carbon atoms of the aryl group is preferably 6 to 15, and morepreferably 6 to 10, from the viewpoint of availability.

Examples of the aryl group (that is substituted or unsubstituted)include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, ananthranyl group, and the like.

A substituent that may substitute the aryl group (that is substituted orunsubstituted) is not particularly limited as long as the substituentdoes not hinder the polymerization reaction. Examples of the substituentinclude those mentioned above in connection with the cycloalkyl group(that is substituted or unsubstituted).

The number of carbon atoms of the heteroaromatic ring group (that issubstituted or unsubstituted) that may be represented by R¹ is normally1 to 15. The number of carbon atoms of the heteroaromatic ring group ispreferably 3 to 15, and more preferably 4 to 10, from the viewpoint ofavailability.

Examples of the heteroaromatic ring group (that is substituted orunsubstituted) include a 5-membered heteroaromatic ring group such as apyrrolyl group, an imidazolyl group, a furyl group, a thienyl group, anoxazolyl group, and a thiazolyl group; a 6-membered heteroaromatic ringgroup such as a pyridyl group, a pyrimidyl group, a pyridazyl group, anda pyrazinyl group; a fused heteroaromatic ring group such as abenzimidazolyl group, a quinolyl group, and a benzofuranyl group; andthe like.

A substituent that may substitute the heteroaromatic ring group (that issubstituted or unsubstituted) is not particularly limited as long as thesubstituent does not hinder the polymerization reaction. Examples of thesubstituent include those mentioned above in connection with thecycloalkyl group (that is substituted or unsubstituted).

Each of R² and R³ in the formula (1) independently represents an atom ora group selected from a hydrogen atom, an aliphatic hydrocarbon group, asubstituted or unsubstituted aryl group, a substituted or unsubstitutedheteroaromatic ring group, a halogen atom, a carboxyl group, ahydrocarbyloxycarbonyl group, a cyano group, and an amide group. Amongthese, a hydrogen atom and an aliphatic hydrocarbon group are preferableas R² and R³.

The number of carbon atoms of the aliphatic hydrocarbon group that maybe represented by R² and R³ is preferably 1 to 10, more preferably 1 to8, and still more preferably 1 to 5.

Examples of the aliphatic hydrocarbon group that may be represented byR² and R³ include an alkyl group having 1 to 10 carbon atoms, such as amethyl group and an ethyl group; an alkenyl group having 2 to 10 carbonatoms, such as a 1-propenyl group and a 2-propenyl group; an alkynylgroup having 2 to 10 carbon atoms, such as a 1-propynyl group and a2-propynyl group; a cycloalkyl group having 3 to 10 carbon atoms, suchas a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and acyclohexyl group; and the like.

Specific examples of the substituted or unsubstituted aryl group thatmay be represented by R² and R³ include those mentioned above inconnection with the substituted or unsubstituted aryl group that may berepresented by R¹.

Specific examples of the substituted or unsubstituted heteroaromaticring group that may be represented by R² and R³ include those mentionedabove in connection with the substituted or unsubstituted heteroaromaticring group that may be represented by R¹.

Examples of the halogen atom that may be represented by R² and R³include a fluorine atom, a chlorine atom, a bromine atom, an iodineatom, and the like.

The number of carbon atoms of the hydrocarbyloxycarbonyl group that maybe represented by R² and R³ is preferably 2 to 10, more preferably 2 to8, and still more preferably 2 to 5.

Examples of the hydrocarbyloxycarbonyl group that may be represented byR² and R³ include an alkyloxycarbonyl group such as a methyloxycarbonylgroup and an ethyloxycarbonyl group; an alkenyloxycarbonyl group such asan ethenyloxycarbonyl group and a 2-propenyloxycarbonyl group; analkynyloxycarbonyl group such as a propagyloxycarbonyl group; asubstituted or unsubstituted aryloxycarbonyl group such as aphenoxycarbonyl group, a 4-methylphenyloxycarbonyl group, a4-chlorophenoxycarbonyl group, a 1-naphthyloxycarbonyl group, and a2-naphthyloxycarbonyl group; and the like.

Examples of the amide group that may be represented by R² and R³ includea group represented by —C(X)—N(r¹)(r²) (wherein X represents an oxygenatom, a sulfur atom, or a selenium atom, and each of r¹ and r²independently represents a hydrogen atom or an organic group having 1 to10 carbon atoms), a group represented by —SO₂-N(r¹)(r²) (wherein r¹ andr² are the same as defined above), and a group represented by—N(r¹)-C(O)-(r²) (wherein r¹ and r² are the same as defined above).

Examples of the organic group that may be represented by r¹ and r²include a linear or branched alkyl group having 1 to 10 carbon atoms,such as a methyl group and an ethyl group; a linear or branched alkenylgroup having 2 to 10 carbon atoms, such as a 1-propenyl group and a2-propenyl group; a linear or branched alkynyl group having 2 to 10carbon atoms, such as a 1-propynyl group and a 2-propynyl group; acycloalkyl group having 3 to 10 carbon atoms, such as a cyclopropylgroup, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;an aryl group having 6 to 10 carbon atoms, such as a phenyl group and a1-naphthyl group; an alkylcarbonyl group having 2 to 10 carbon atoms,such as an acetyl group; an alkoxycarbonyl group having 2 to 10 carbonatoms, such as a methoxycarbonyl group; a hydrocarbylsulfonyl grouphaving 1 to 10 carbon atoms, such as a methylsulfonyl group and ap-toluenesulfonyl group; and the like.

Examples of the group represented by —C(X)—N(r¹)(r²) include anaminocarbonyl group, a methylaminocarbonyl group, an ethylaminocarbonylgroup, a benzylaminocarbonyl group, a phenylaminocarbonyl group, adimethylaminocarbonyl group, a phenylmethylaminocarbonyl group, adimethylaminothiocarbonyl group, a dimethylaminoselenocarbonyl group,and the like.

Examples of the group represented by —SO₂-N(r¹)(r²) include anaminosulfonyl group, a methylaminosulfonyl group, a benzylaminosulfonylgroup, a dimethylaminosulfonyl group, and the like.

Examples of the group represented by —N(r¹)-C(O)-(r²) include anacetylamino group, a benzoylamino group, and the like.

Each of R⁴, R⁵, and R⁶ in the formula (1) independently represents anatom or a group selected from a hydrogen atom, an aliphatic hydrocarbongroup, a substituted or unsubstituted aryl group, a substituted orunsubstituted heteroaromatic ring group, a halogen atom, a carboxylgroup, a hydrocarbyloxycarbonyl group, a cyano group, an amide group,and a group represented by the formula (2). Among these, a hydrogenatom, an aliphatic hydrocarbon group (including a ring that is formed byR⁴ and R⁵ that are bonded to each other), a hydrocarbyloxycarbonylgroup, and the group represented by the formula (2) are preferable asR⁴, R⁵, and R⁶.

Specific examples of the aliphatic hydrocarbon group that may berepresented by R⁴, R⁵, and R⁶ include those mentioned above inconnection with the aliphatic hydrocarbon group that may be representedby R² and R³.

Specific examples of the substituted or unsubstituted aryl group thatmay be represented by R⁴, R⁵, and R⁶ include those mentioned above inconnection with the substituted or unsubstituted aryl group that may berepresented by R¹.

Specific examples of the substituted or unsubstituted heteroaromaticring group that may be represented by R⁴, R⁵, and R⁶ include thosementioned above in connection with the substituted or unsubstitutedheteroaromatic ring group that may be represented by R¹.

Specific examples of the halogen atom that may be represented by R⁴, R⁵,and R⁶ include those mentioned above in connection with the halogen atomthat may be represented by R² and R³.

Specific examples of the hydrocarbyloxycarbonyl group that may berepresented by R⁴, R⁵, and R⁶ include those mentioned above inconnection with the hydrocarbyloxycarbonyl group that may be representedby R² and R³.

Specific examples of the amide group that may be represented by R⁴, R⁵,and R⁶ include those mentioned above in connection with the amide groupthat may be represented by R² and R³.

R⁷ in the formula (2) represents a group selected from an alkyl group, asubstituted or unsubstituted cycloalkyl group, a substituted orunsubstituted aryl group, and a substituted or unsubstitutedheteroaromatic ring group. Among these, an alkyl group and a substitutedor unsubstituted aryl group are preferable as R⁷.

Specific examples of the alkyl group, the substituted or unsubstitutedcycloalkyl group, the substituted or unsubstituted aryl group, and thesubstituted or unsubstituted heteroaromatic ring group that may berepresented by R⁷ include those mentioned above in connection with thealkyl group, the substituted or unsubstituted cycloalkyl group, thesubstituted or unsubstituted aryl group, and the substituted orunsubstituted heteroaromatic ring group that may be represented by R¹.

Each of R⁸ and R⁹ in the formula (2) independently represents an atom ora group selected from a hydrogen atom, an aliphatic hydrocarbon group, asubstituted or unsubstituted aryl group, a substituted or unsubstitutedheteroaromatic ring group, a halogen atom, a carboxyl group, ahydrocarbyloxycarbonyl group, a cyano group, and an amide group. Amongthese, a hydrogen atom and an aliphatic hydrocarbon group are preferableas R⁸ and R⁹.

Specific examples of the aliphatic hydrocarbon group, the substituted orunsubstituted aryl group, the substituted or unsubstitutedheteroaromatic ring group, the halogen atom, the hydrocarbyloxycarbonylgroup, and the amide group that may be represented by R⁸ and R⁹ includethose mentioned above in connection with the aliphatic hydrocarbongroup, the substituted or unsubstituted aryl group, the substituted orunsubstituted heteroaromatic ring group, the halogen atom, thehydrocarbyloxycarbonyl group, and the amide group that may berepresented by R² and R³.

Note that two groups selected from R² to R⁶ are optionally bonded toeach other to form a ring other than an aromatic ring. A hydrocarbonring is preferable as the ring other than an aromatic ring.

The ring is preferably a 5 to 7-membered ring, and more preferably a6-membered ring.

Examples of the ring when the ring includes a double bond (e.g., when R³and R⁶ or R⁴ and R⁵ are bonded to each other), include a substituted orunsubstituted cyclopentene ring, a substituted or unsubstitutedcyclohexene ring, a substituted or unsubstituted cycloheptene ring, andthe like.

Examples of the ring when the ring does not include a double bond (e.g.,when R⁵ and R⁶ are bonded to each other), include a substituted orunsubstituted cyclopentane ring, a substituted or unsubstitutedcyclohexane ring, a substituted or unsubstituted cycloheptane ring, andthe like.

Examples of a substituent that may substitute the ring include thosementioned above in connection with the substituent that may substituteR² to R⁶.

Specific examples of the organotellurium compound represented by theformula (1) include 3-methyltellanyl-1-propene,3-methyltellanyl-2-methyl-1-propene,3-methyltellanyl-2-phenyl-1-propene,3-methyltellanyl-3-methyl-1-propene,3-methyltellanyl-3-phenyl-1-propene,3-methyltellanyl-3-cyclohexyl-1-propene,3-methyltellanyl-3-cyano-1-propene, 3-ethyltellanyl-1-propene,3-methyltellanyl-3-dimethylaminocarbonyl-1-propene,3-[(n-propyl)tellanyl]-1-propene, 3-isopropyltellanyl-1-propene,3-(n-butyl)tellanylpropene, 3-[(n-hexyl)tellanyl]-1-propene,3-phenyltellanyl-1-propene, 3-[(p-methylphenyl)tellanyl]-1-propene,3-cyclohexyltellanyl-1-propene, 3-[(2-pyridyl)tellanyl]-1-propene,3-methyltellanyl-2-butene, 3-methyltellanyl-1-cyclopentene,3-methyltellanyl-1-cyclohexene, 3-methyltellanyl-1-cyclooctene,3-ethyltellanyl-1-cyclohexene, 3-methyltellanyl-1-cyclohexene,3-[(n-propyl)tellanyl]-1-cyclohexene,3-([n-butyl)tellanyl]-1-cyclohexene, methyl2-(methyltellanylmethyl)acrylate, ethyl2-(methyltellanylmethyl)acrylate, n-butyl2-(methyltellanylmethyl)acrylate, methyl2-(ethyltellanylmethyl)acrylate, methyl2-([n-butyl)tellanylmethyl]acrylate, methyl2-(cyclohexyltellanylmethyl)acrylate, 1,4-bis(methyltellanyl)-2-butene,1,4-bis(ethyltellanyl)-2-butene, 1,4-bis[(n-butyl)tellanyl]-2-butene,1,4-bis(cyclohexyltellanyl)-2-butene, 1,4-bis(phenyltellanyl)-2-butene,and the like. Note that the organotellurium compound used in connectionwith one embodiment of the invention is not limited to theseorganotellurium compounds.

The organotellurium compound represented by the formula (1) may beobtained by reacting a compound represented by the following formula(4), a compound represented by the following formula (5), and metallictellurium according to the method disclosed in WO2004/014962, forexample.

Note that R² to R⁶ in the formula (4) are the same as defined above. Xrepresents a halogen atom. The halogen atom represented by X may be afluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Amongthese, a chlorine atom and a bromine atom are preferable.

R¹ in the formula (5) is the same as defined above. M represents analkali metal such as lithium, sodium, or potassium, an alkaline-earthmetal such as magnesium or calcium, or copper. m is 1 when M representsan alkali metal, is 2 when M represents an alkaline-earth metal, and is1 or 2 when M represents copper. When M in the formula (5) representsmagnesium, one of the two groups represented by R¹ may be a halogenatom. Specifically, the compound represented by the formula (5) may be aGrignard reagent.

More specifically, metallic tellurium is suspended in a solvent in aninert gas atmosphere to prepare a suspension, and the compoundrepresented by the formula (5) is added to the suspension to effect areaction. The compound represented by the formula (4) is added to theresulting reaction mixture to effect a reaction to obtain theorganotellurium compound represented by the formula (1).

The compound represented by the formula (5) is normally used in anamount of 0.5 to 1.5 mol, and preferably 0.8 to 1.2 mol, based on 1 molof metallic tellurium.

The compound represented by the formula (4) is normally used in anamount of 0.5 to 1.5 mol, and preferably 0.8 to 1.2 mol, based on 1 molof metallic tellurium.

Examples of the inert gas include nitrogen gas, helium gas, argon gas,and the like.

Examples of the solvent include an ether-based solvent such as diethylether and tetrahydrofuran; an amide-based solvent such asdimethylformamide; an aromatic solvent such as toluene; an aliphatichydrocarbon-based solvent such as hexane; and the like.

Each of the compound represented by the formula (5) and the compoundrepresented by the formula (4) is preferably added dropwise to thereaction system at a low temperature (−20 to 5° C.).

The reaction conditions are not particularly limited. For example, thereaction time is set to 5 minutes to 24 hours, and the reactiontemperature is set to −20 to 80° C.

Organotellurium compounds respectively represented by the followingformulas (1a) to (1c) may be obtained as follows.

wherein R¹ to R⁹ are the same as defined above.

Specifically, the organotellurium compounds respectively represented bythe formulas (1a) to (1c) may be obtained by reacting compoundsrespectively represented by the following formulas (4a) to (4c) asdescribed above instead of the compound represented by the formula (4).

wherein R² to R⁹ are the same as defined above, provided that R⁴, R⁵,and R⁶ are not the group represented by the formula (2), and X¹ and X²represent a halogen atom (preferably a chlorine atom or a bromine atom).

When using the compounds respectively represented by the formulas (4a)to (4c), the compounds respectively represented by the formulas (4a) to(4c) are normally used in an amount of 0.25 to 0.75 mol, and preferably0.4 to 0.6 mol, based on 1 mol of metallic tellurium. The compoundrepresented by the formula (5) is normally used in an amount of 0.5 to1.5 mol, and preferably 0.8 to 1.2 mol, based on 1 mol of metallictellurium.

After completion of the reaction, the target product may be isolated bya known post-treatment operation and separation-purification means. Forexample, the reaction mixture is sequentially washed with deaeratedwater, a deaerated ammonium chloride aqueous solution, and a deaeratedsaturated sodium chloride solution, and the organic layer is dried andconcentrated to obtain a crude product. The resulting reaction productis optionally purified using a known purification method (e.g., vacuumdistillation method) to obtain the target organotellurium compoundhaving high purity.

The organotellurium compound represented by the formula (1) that is usedas the radical polymerization initiator according to one embodiment ofthe invention includes at least one non-aromatic carbon-carbon doublebond at the β-position with respect to Te.

When a radically polymerizable monomer is subjected to radicalpolymerization in the presence of the organotellurium compoundrepresented by the formula (1), the carbon-carbon double bond isintroduced into the polymerization-initiation terminal, and a livingradical polymerization reaction with excellent controllability can beimplemented (described later).

Therefore, it is possible to efficiently produce a polymer that includesa double bond at the molecular terminal by utilizing the radicalpolymerization initiator according to one embodiment of the invention.

2) Method for Producing Polymer

A method for producing a polymer according to one embodiment of theinvention includes subjecting a radically polymerizable monomer toradical polymerization in a state in which the radical polymerizationinitiator according to one embodiment of the invention is present in apolymerization system (i.e., in the presence of the radicalpolymerization initiator according to one embodiment of the invention).

The radically polymerizable monomer used in connection with oneembodiment of the invention is not particularly limited as long as it isradically polymerizable. Examples of the radically polymerizable monomerinclude an acrylic-based monomer such as methyl (meth)acrylate, ethyl(meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, octyl(meth)acrylate, lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, isobornyl(meth)acrylate, cyclododecyl (meth)acrylate, glycidyl (meth)acrylate,(meth)acrylic acid, (meth)acrylamide, N-methyl(meth)acrylamide,N-isopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide,N-(2-dimethylaminoethyl)(meth)acrylamide,N-(3-dimethylaminopropyl)(meth)acrylamide, 2-(dimethylamino)ethyl(meth)acrylate, 3-dimethylaminopropyl (meth)acrylate, hydroxyethyl(meth)acrylate, (meth)acrylonitrile,2-hydroxy-3-(meth)acryloyloxypropyltrimethylammonium chloride, and(meth)acryloylaminoethyldimethylbenzylammonium chloride (Note that theterm “(meth)acrylic acid” used herein refers to acrylic acid ormethacrylic acid (this definition also applies to (meth)acrylamide andthe like));

a styrene-based monomer such as styrene, a-methylstyrene,2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-methoxy styrene,4-tert-butylstyrene, 4-n-butylstyrene, 4-tert-butoxystyrene,2-hydroxymethylstyrene, 2-chlorostyrene, 4-chlorostyrene,2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene,4-styrenesulfonic acid, and an alkali metal salt (e.g., sodium salt andpotassium salt) thereof; an a-olefin-based monomer such as ethylene,propene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene;a vinyl-based monomer such as 2-vinylthiophene, N-methyl-2-vinylpyrrole,1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine,N-vinylformamide,

N-vinylacetamide, vinyl acetate, vinyl benzoate, methyl vinyl ketone,vinyl chloride, and vinylidene chloride;

an unsaturated carboxylic acid-based monomer such as maleic acid,fumaric acid, itaconic acid, citraconic acid, crotonic acid, and maleicanhydride;

a conjugated diene-based monomer such as 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 1,3-pentadiene;a non-conjugated diene-based monomer such as 4-methyl-1,4-hexadiene and7-methyl-1,6-octadiene; and the like.

These radically polymerizable monomers may be used either alone or incombination.

The method for producing a polymer according to one embodiment of theinvention can implement a controlled polymerization reaction using awide variety of radically polymerizable monomers as compared with knownatom transfer radical polymerization that utilizes an allyl halide as apolymerization initiator to introduce a carbon-carbon double bond intothe polymerization-initiation terminal. Therefore, the method forproducing a polymer according to one embodiment of the invention canparticularly suitably be used when using a radically polymerizablemonomer for which it is difficult to implement a controlledpolymerization reaction using a known method. The radicallypolymerizable monomer that is particularly suitably used whenimplementing the method for producing a polymer according to oneembodiment of the invention includes at least one radicallypolymerizable monomer selected from (meth)acrylates that include afunctional group selected from a hydroxyl group, an amino group, and anammonium group, (meth)acrylic acids, (meth)acrylamides, α-olefins, avinyl-based monomer that includes a vinyl group that is not conjugate toan aromatic ring, and a conjugated diene-based monomer.

The amount of the organotellurium compound represented by the formula(1) and the amount of the radically polymerizable monomer may beappropriately adjusted taking account of the molecular weight and themolecular weight distribution of the desired polymer. Theorganotellurium compound represented by the formula (1) is normally usedin an amount of 0.00005 to 0.2 mol, and preferably 0.0001 to 0.02 mol,based on 1 mol of the radically polymerizable monomer.

Radical polymerization may be effected by charging a container (in whichthe internal atmosphere has been replaced by an inert gas (e.g.,nitrogen gas, helium gas, or argon gas) with the organotelluriumcompound represented by the formula (1), the radically polymerizablemonomer, and an optional solvent, and stirring the mixture at a specifictemperature for a specific time.

A solvent that is normally used for a radical polymerization reactionmay be used as the solvent. Examples of the solvent include aromatichydrocarbons such as benzene and toluene; ketones such as acetone andmethyl ethyl ketone; esters such as ethyl acetate; ethers such asdioxane and tetrahydrofuran (THF); amides such as N,N-dimethylformamide(DMF); sulfur-containing compounds such as dimethyl sulfoxide (DMSO);alcohols such as methanol, ethanol, isopropanol, and n-butanol;halogen-containing compounds such as chloroform, carbon tetrachloride,and trifluoromethylbenzene; cellosolve and a derivative thereof such asethyl cellosolve, butyl cellosolve, and 1-methoxy-2-propanol; water; andthe like.

These solvents may be used either alone or in combination. When usingthe solvent, the solvent is used in an amount of 0.01 to 50 mL,preferably 0.05 to 10 mL, and more preferably 0.1 to 5 mL, based on 1 gof the radically polymerizable monomer, for example.

The reaction temperature and the reaction time may be appropriatelyadjusted. The reaction temperature is normally set to 20 to 150° C., andpreferably 40 to 100° C., and the reaction time is normally set to 1minute to 100 hours, and preferably 0.1 to 30 hours.

The reaction is normally effected under normal pressure. Note that thereaction may be effected under pressure, or may be effected underreduced pressure.

When implementing the method for producing a polymer according to oneembodiment of the invention, the radically polymerizable monomer may besubjected to radical polymerization in a state in which an azo-basedradical generator is further present in the polymerization system.

When the polymerization reaction is effected in the presence of theazo-based radical generator, the polymerization reaction is furtherpromoted, and a polymer can be efficiently obtained.

An arbitrary azo-based radical generator that is normally used forradical polymerization as a polymerization initiator or a polymerizationpromoter may be used as the azo-based radical generator.

Examples of the azo-based radical generator include 2,2′-azobis(isobutylonitrile) (AIBN), 2,2′ -azobis(2-methylbutyronitrile)(AMBN), 2,2′ -azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis(cyclohexane-1-carbonitrile) (ACHN), dimethyl 2,2′-azobisisobutyrate (MAIB), 4,4′-azobis(4-cyanovaleric acid) (ACVA),1,1′-azobis(1-acetoxy-1-phenylethane), 2,2′-azobis(2-methylbutylamide),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),2,2′-azobis(2-methylamidinopropane) dihydrochloride,2,2′-azobis[2-(2-imidazolin-2-yl)propane],2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide],2,2′-azobis(2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide,2,2′-azobis(N-butyl-2-methylpropionamide),2,2′-azobis(N-cyclohexyl-2-methylpropionamide), and the like.

These azo-based radical generators may be used either alone or incombination.

It is preferable to appropriately select the azo-based radical generatortaking account of the reaction conditions.

For example, 2,2′-azobis(2,4-dimethylvaleronitrile) (ADVN) and2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) are preferable wheneffecting the polymerization reaction at a low temperature (40° C. orless). 2,2′-Azobis(isobutylonitrile) (AIBN),2,2′-azobis(2-methylbutyronitrile) (AMBN), dimethyl2,2′-azobisisobutyrate (MAIB), and 1,1′-azobis(1-acetoxy-1-phenylethane) are preferable when effecting the polymerizationreaction at a medium temperature (40 to 80° C.).1,1′-Azobis(cyclohexane-1-carbonitrile) (ACHN),2-cyano-2-propylazoformamide, 2,2′-azobis(N-butyl-2-methylpropionamide),2,2′-azobis(N-cyclohexyl-2-methylpropionamide), and2,2′-azobis(2,4,4-trimethylpentane) are preferable when effecting thepolymerization reaction at a high temperature (80° C. or more).

When using the azo-based radical generator, the azo-based radicalgenerator is used in an amount of 0.01 to 100 mol, preferably 0.05 to 10mol, and more preferably 0.05 to 2 mol, based on 1 mol of theorganotellurium compound represented by the formula (1).

When implementing the method for producing a polymer according to oneembodiment of the invention, the polymerization reaction may be effectedin a state in which light is applied to the polymerization system (i.e.,while applying light to the polymerization system).

When the polymerization reaction is effected in a state in which lightis applied to the polymerization system, the polymerization reaction isfurther promoted, and a polymer can be efficiently obtained.

Ultraviolet rays (light having a wavelength of 200 to 380 nm) or visiblelight (light having a wavelength of 380 to 830 nm) is preferable aslight applied to the polymerization system. Light may be applied to thepolymerization system using a method that is normally used wheneffecting a photopolymerization reaction. For example, light may beapplied to the polymerization system using a light source such as alow-pressure mercury lamp, a medium-pressure mercury lamp, ahigh-pressure mercury lamp, an ultra-high-pressure mercury lamp, achemical lamp, a black light lamp, a microwave-excited mercury lamp, ametal halide lamp, a xenon lamp, a krypton lamp, or an LED lamp.

Note that the azo-based radical generator and the application of lightmay be used in combination. However, the polymerization reaction isnormally promoted sufficiently when either the azo-based radicalgenerator or the application of light is used.

When implementing the method for producing a polymer according to oneembodiment of the invention, the radically polymerizable monomer may besubjected to radical polymerization in a state in which the ditelluridecompound represented by the formula (3) is further present in thepolymerization system.

When the polymerization reaction is effected in the presence of theditelluride compound represented by the formula (3), it is possible tomore advantageously control the polymerization reaction, and obtain apolymer having a molecular weight close to the theoretical value and anarrow molecular weight distribution.

Each of R¹⁰ and R¹¹ in the formula (3) independently represents a groupselected from an alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted aryl group, and a substituted orunsubstituted heteroaromatic ring group. Specific examples of the alkylgroup, the substituted or unsubstituted cycloalkyl group, thesubstituted or unsubstituted aryl group, and the substituted orunsubstituted heteroaromatic ring group that may be represented by R¹⁰and R¹¹ include those mentioned above in connection with the alkylgroup, the substituted or unsubstituted cycloalkyl group, thesubstituted or unsubstituted aryl group, and the substituted orunsubstituted heteroaromatic ring group that may be represented by R¹.

Specific examples of the ditelluride compound represented by the formula(3) include dimethyl ditelluride, diethyl ditelluride, di(n-propyl)ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride,di(n-butyl) ditelluride, di(sec-butyl) ditelluride, di(tert-butyl)ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride,bis(p-methoxyphenyl) ditelluride, bis(p-aminophenyl) ditelluride,bis(p-nitrophenyl) ditelluride, bis(p-cyanophenyl) ditelluride,bis(p-sulfonylphenyl) ditelluride, bis(2-naphthyl) ditelluride,4,4′-dypyridyl ditelluride, and the like.

These ditelluride compounds may be used either alone or in combination.

When using the ditelluride compound represented by the formula (3), theditelluride compound represented by the formula (3) is used in an amountof 0.01 to 100 mol, preferably 0.1 to 10 mol, and more preferably 0.1 to5 mol, based on 1 mol of the organotellurium compound represented by theformula (1), for example.

Note that the ditelluride compound represented by the formula (3) may beused in combination with the azo-based radical generator, or may be usedin combination with the application of light.

After completion of the reaction, the polymer may be isolated andpurified using an ordinary method. For example, the solvent and theresidual radically polymerizable monomer may be evaporated from thereaction solution under reduced pressure to isolate the polymer, or thereaction solution may be poured into a poor solvent to precipitate thepolymer.

The molecular weight of a polymer that is obtained by the method forproducing a polymer according to one embodiment of the invention can beadjusted by adjusting the reaction time and the amount oforganotellurium compound. For example, the number average molecularweight of the polymer is 500 to 1,000,000, and preferably 1,000 to50,000. The molecular weight distribution (Mw/Mn) of the polymer isnormally 1.01 to 2.50, preferably 1.01 to 2.00, more preferably 1.01 to1.50, still more preferably 1.01 to 1.30, and most preferably 1.01 to1.15.

The method for producing a polymer according to one embodiment of theinvention can produce a copolymer when two or more radicallypolymerizable monomers are used.

For example, the method for producing a polymer according to oneembodiment of the invention can produce a random copolymer when two ormore radically polymerizable monomers are simultaneously present in thepolymerization system.

The method for producing a polymer according to one embodiment of theinvention can produce a block copolymer when two or more radicallypolymerizable monomers are sequentially reacted, since thepolymerization reaction proceeds in a living manner (described later).

The growing terminal of the polymer chain during the polymerizationreaction effected by the method for producing a polymer according to oneembodiment of the invention is a highly reactive organotellurium site(R¹-Te- or R⁷-Te-) derived from the radical polymerization initiatoraccording to one embodiment of the invention, and has living properties.

When the growing terminal of the polymer chain that has livingproperties is exposed to air, the growing terminal is substituted with ahydrogen atom or a hydroxyl group, and is inactivated.

The other terminal (polymerization-initiation terminal) of the polymerobtained by the method for producing a polymer according to oneembodiment of the invention is a group represented by(R⁵)(R⁶)C═C(R⁴)-C(R²)(R³)- that is derived from the organotelluriumcompound represented by the formula (1).

Therefore, the method for producing a polymer according to oneembodiment of the invention can efficiently produce a polymer thatincludes a double bond at the molecular terminal, has a controlledmolecular weight and molecular weight distribution, and is useful as amacromonomer and the like.

EXAMPLES

The invention is further described below by way of examples and thelike.

Note that the invention is not limited to the following examples and thelike. Note that the units “parts” and “%” respectively refer to “partsby weight” and “wt %” unless otherwise indicated.

The measurement methods used in connection with the examples aredescribed below.

¹H-NMR measurement

The ¹H-NMR measurement was performed using an NMR spectrometer“BRUKER-500” (manufactured by BRUKER) (solvent: CDCl₃ or d-DMSO).

Gas Chromatography Measurement

The gas chromatography measurement was performed using a gaschromatograph “GC2010” (manufactured by Shimadzu Corporation) and acolumn “ZB-5” (manufactured by Phenomenex). The quantitativedetermination was performed based on an internal standard method usingmesitylene.

Gel Permeation Chromatography (GPC) Measurement

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of thepolymer were determined as polystyrene-equivalent values by gelpermeation chromatography (GPC) measurement using a GPC system“HLC-8220” (manufactured by Tosoh Corporation) (column: TSK-GELG6000HHR, G5000HHR, G4000HHR, and G2500HHR (manufactured by TosohCorporation) (that were sequentially connected), eluent: tetrahydrofuran(THF)).

Synthesis Example 1

A 300 mL three-necked flask was charged with 5.23 g (41 mmol) ofmetallic tellurium (manufactured by Aldrich (hereinafter the same)) and45 mL of THF in a nitrogen atmosphere to prepare a suspension. Thesuspension was cooled to 0° C. with stirring. 45.0 mL (43.0 mmol) ofmethyllithium (1.10 M diethyl ether solution, manufactured by KantoChemical Co., Inc. (hereinafter the same)) was added dropwise to thesuspension over 10 minutes while cooling the suspension with stirring.After the dropwise addition, the mixture contained in the three-neckedflask was stirred at room temperature (25° C.) for 20 minutes to obtaina reaction solution in which the metallic tellurium had completelydisappeared.

30 mL of a saturated NH₄Cl aqueous solution was added to the reactionsolution with stirring, and the mixture was stirred for 1 hour in air.The organic layer was separated, and sequentially washed with water anda saturated NaCl aqueous solution. The organic layer (i.e., the reactionsolution subjected to washing) was dried over anhydrous magnesiumsulfate, and filtered through Celite. The filtrate was concentratedunder reduced pressure, and the concentrate was subjected to vacuumdistillation (0.6 mmHg, 43° C.) to obtain 2.48 g (yield: 42%) ofdimethyl ditelluride as a brown oily product.

The ¹H-NMR data of the resulting dimethyl ditelluride is shown below.¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm) 2.67 (s, 6H)

Synthesis Example 2

A 300 mL three-necked flask was charged with 8.75 g (68.6 mmol) ofmetallic tellurium and 90 mL of THF in a nitrogen atmosphere to preparea suspension. The suspension was cooled to 0° C. with stirring. 45.0 mL(72.0 mmol) of n-butyllithium (1.6 M hexane solution, manufactured byKanto Chemical Co., Inc. (hereinafter the same)) was added dropwise tothe suspension over 10 minutes while cooling the suspension withstirring. After the dropwise addition, the mixture contained in thethree-necked flask was stirred at room temperature (25° C.) for 20minutes to obtain a reaction solution in which the metallic telluriumhad completely disappeared.

50 mL of a saturated NH₄Cl aqueous solution was added to the reactionsolution with stirring, and the mixture was stirred for 1 hour in air.The organic layer was separated, and sequentially washed with water anda saturated NaCl aqueous solution.

The organic layer (i.e., the reaction solution subjected to washing) wasdried over anhydrous magnesium sulfate, and filtered through Celite. Thefiltrate was concentrated under reduced pressure, and the concentratewas subjected to vacuum distillation (0.2 mmHg, 84° C.) to obtain 4.98 g(yield: 39%) of dibutyl ditelluride as a brown oily product.

The ¹H-NMR data of the resulting dibutyl ditelluride is shown below.¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm) 0.93 (t, J=7.4 Hz, 3H), 1.35-1.43(m, 4H), 1.67-1.74 (m, 4H), 3.11 (t, J=7.4 Hz, 4H)

Example 1

A 300 mL three-necked flask was charged with 11.48 g (90 mmol) ofmetallic tellurium and 86 mL of THF in a nitrogen atmosphere to preparea suspension. The suspension was cooled to 0° C. with stirring. 86.0 mL(94.5 mmol) of methyllithium (1.10 M diethyl ether solution) was addeddropwise to the suspension over 10 minutes while cooling the suspensionwith stirring. After the dropwise addition, the mixture contained in thethree-necked flask was stirred at room temperature (25° C.) for 20minutes to obtain a reaction solution in which the metallic telluriumhad completely disappeared.

The reaction solution was cooled to 0° C. with stirring. 11.4 g (94.5mmol) of allyl bromide (manufactured by Tokyo Chemical Industry Co.,Ltd. (hereinafter the same)) was added to the reaction solution whilecooling the reaction solution with stirring. After reacting the mixturecontained in the three-necked flask for 2 hours with stirring, thereaction solution was returned to room temperature.

The resulting reaction solution was sequentially washed with deaeratedwater, a deaerated saturated NH₄Cl aqueous solution, and a deaeratedsaturated NaCl aqueous solution. The organic layer (i.e., the reactionsolution subjected to washing) was dried over anhydrous magnesiumsulfate, and filtered through Celite in a nitrogen atmosphere.

The filtrate was concentrated under reduced pressure, and theconcentrate was subjected to vacuum distillation (33 mmHg, 55° C.) toobtain 6.55 g (yield: 40%) of 3-methyltellanyl-1-propene as a yellowoily product.

The ¹H-NMR data of the resulting 3-methyltellanyl-1-propene is shownbelow. ¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm) 1.85 (s, 3H), 3.31 (d, J=8.5Hz, 2H), 4.80 (d,

J=9.0 Hz, 1H), 4.85 (d, J=17.0 Hz, 1H), 5.90-5.99 (m, 1H)

Example 2

A 300 mL three-necked flask was charged with 6.38 g (50 mmol) ofmetallic tellurium and 50 mL of THF in a nitrogen atmosphere to preparea suspension. The suspension was cooled to 0° C. with stirring. 48.6 mL(52.5 mmol) of phenyllithium (1.08 M cyclohexane-diethyl ether solution,manufactured by Kanto Chemical Co., Inc.) was added dropwise to thesuspension over 10 minutes while cooling the suspension with stirring.After the dropwise addition, the mixture contained in the three-neckedflask was stirred at room temperature (25° C.) for 20 minutes to obtaina reaction solution in which the metallic tellurium had completelydisappeared.

The reaction solution was cooled to 0° C. with stirring. 6.35 g (52.5mmol) of allyl bromide was added to the reaction solution while coolingthe reaction solution with stirring. After reacting the mixturecontained in the three-necked flask for 2 hours with stirring, thereaction solution was returned to room temperature.

The resulting reaction solution was sequentially washed with deaeratedwater, a deaerated saturated NH₄Cl aqueous solution, and a deaeratedsaturated NaCl aqueous solution. The organic layer (i.e., the reactionsolution subjected to washing) was dried over anhydrous magnesiumsulfate, and filtered through Celite in a nitrogen atmosphere. Thefiltrate was concentrated under reduced pressure, and the concentratewas subjected to vacuum distillation (2.0 mmHg, 70° C.) to obtain 5.6 g(yield: 46%) of 3-phenyltellanyl-1-propene as a yellow oily product.

The ¹H-NMR data of the resulting 3-phenyltellanyl-1-propene is shownbelow. ¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm) 3.63 (dd, 2H), 4.77 (d,J=10.0 Hz, 1H), 4.83 (dd, J=16.8 Hz, 1H), 6.03-6.12 (m, 1H), 7.18-7.78(m, 5H)

Example 3

A 300 mL three-necked flask was charged with 3.76 g (29.5 mmol) ofmetallic tellurium and 38 mL of THF in a nitrogen atmosphere to preparea suspension. The suspension was cooled to 0° C. with stirring. 19.4 mL(31.0 mmol) of n-butyllithium (1.6 M hexane solution) was added dropwiseto the suspension over 10 minutes while cooling the suspension withstirring. After the dropwise addition, the mixture contained in thethree-necked flask was stirred at room temperature (25° C.) for 20minutes to obtain a reaction solution in which the metallic telluriumhad completely disappeared.

The reaction solution was cooled to 0° C. with stirring. 5.0 g (31.0mmol) of 3-bromocyclohexene (manufactured by Tokyo Chemical IndustryCo., Ltd.) was added to the reaction solution while cooling the reactionsolution with stirring. After reacting the mixture contained in thethree-necked flask for 2 hours with stirring, the reaction solution wasreturned to room temperature.

The resulting reaction solution was sequentially washed with deaeratedwater, a deaerated saturated NH₄Cl aqueous solution, and a deaeratedsaturated NaCl aqueous solution. The organic layer (i.e., the reactionsolution subjected to washing) was dried over anhydrous magnesiumsulfate, and filtered through Celite in a nitrogen atmosphere.

The filtrate was concentrated under reduced pressure, and theconcentrate was subjected to vacuum distillation (1.0 mmHg, 82° C.) toobtain 4.47 g (yield: 57%) of 3-[(n-butyl)tellanyl]-1-cyclohexene as ayellow oily product.

The ¹H-NMR data of the resulting 3-[(n-butyl)tellanyl]-1-cyclohexene isshown below.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm) 0.92 (t, J=7.5 Hz, 3H), 1.38 (dt,J=7.5 Hz, 14.8 Hz, 2H), 1.64-1.89 (m, 4H), 2.01-2.22 (m, 4H), 2.62-2.78(m, 2H), 3.96-4.00 (m, 1H), 5.56-5.60 (m, 1H), 5.85-5.89 (m, 1H)

Example 4

A 300 mL three-necked flask was charged with 3.39 g (26.6 mmol) ofmetallic tellurium and 25 mL of THF in a nitrogen atmosphere to preparea suspension. The suspension was cooled to 0° C. with stirring. 25.1 mL(27.9 mmol) of methyllithium (1.11 M diethyl ether solution) was addeddropwise to the suspension over 10 minutes while cooling the suspensionwith stirring. After the dropwise addition, the mixture contained in thethree-necked flask was stirred at room temperature (25° C.) for 20minutes to obtain a reaction solution in which the metallic telluriumhad completely disappeared.

The reaction solution was cooled to 0° C. with stirring. 5.0 g (27.9mmol) of methyl 2-(bromomethyl)acrylate (manufactured by Tokyo ChemicalIndustry Co., Ltd.)

was added to the reaction solution while cooling the reaction solutionwith stirring. After reacting the mixture contained in the three-neckedflask for 2 hours with stirring, the reaction solution was returned toroom temperature.

The resulting reaction solution was sequentially washed with deaeratedwater, a deaerated saturated NH₄Cl aqueous solution, and a deaeratedsaturated NaCl aqueous solution. The organic layer (i.e., the reactionsolution subjected to washing) was dried over anhydrous magnesiumsulfate, and filtered through Celite in a nitrogen atmosphere.

The filtrate was concentrated under reduced pressure, and theconcentrate was subjected to vacuum distillation (1.0 mmHg, 52° C.) toobtain 2.3 g (yield: 36%) of methyl 2-(methyltellanylmethyl)acrylate asa yellow oily product.

The ¹H-NMR data of the resulting methyl 2-(methyltellanylmethyl)acrylateis shown below.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm) 1.91 (s, 3H), 3.74 (s, 2H), 3.76 (s,3H), 5.54 (s, 1H), 6.18 (s, 1H)

Example 5

In a glovebox in which the internal atmosphere had been replaced bynitrogen, a 30 mL glass reaction vessel was charged with 0.68 g (10mmol) of isoprene (manufactured by Tokyo Chemical Industry Co., Ltd.(hereinafter the same)), 0.53 g (10 mmol) of acrylonitrile (manufacturedby Wako Pure Chemical Industries, Ltd. (hereinafter the same)), 36.7 mg(0.20 mmol) of 3-methyltellanyl-1-propene obtained in Example 1, 5.7 mg(0.02 mmol) of dimethyl ditelluride obtained in Synthesis Example 1,24.4 mg (0.10 mmol) of 1,1′-azobis(cyclohexane-1-carbonitrile)(manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter thesame)), and 0.24 g of mesitylene (manufactured by Wako Pure ChemicalIndustries, Ltd. (hereinafter the same)) (gas chromatography internalstandard (hereinafter referred to as “internal standard”)), and themixture was stirred at 80° C. for 16 hours to effect a polymerizationreaction.

The resulting polymerization reaction product was purified byevaporating a volatile component under reduced pressure, and thepurified product was dried to obtain an isoprene-acrylonitrile randomcopolymer.

The conversion ratio of isoprene and the conversion ratio ofacrylonitrile determined by gas chromatography were 93% and 84%,respectively.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of theisoprene-acrylonitrile random copolymer determined by GPC (with respectto a polystyrene standard sample) were 7,060, 6,130, and 1.15,respectively.

It was found by ¹H-NMR analysis that the isoprene-acrylonitrile randomcopolymer included a terminal double bond in a ratio of 98%.

Example 6

A polymerization reaction was effected in the same manner as in Example5, except that 1,1′-azobis(cyclohexane-1-carbonitrile) was not added,and light was applied to the polymerization system during thepolymerization reaction using an LED lamp (output: 6 W, 5% ND filter wasused), to obtain an isoprene-acrylonitrile random copolymer.

The conversion ratio of isoprene and the conversion ratio ofacrylonitrile determined by gas chromatography were 88% and 81%,respectively.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of theisoprene-acrylonitrile random copolymer determined by GPC (with respectto a polystyrene standard sample) were 6,730, 6,100, and 1.09,respectively.

It was found by ¹H-NMR analysis that the isoprene-acrylonitrile randomcopolymer included a terminal double bond in a ratio of 96%.

Example 7

A polymerization reaction was effected in the same manner as in Example5, except that dimethyl ditelluride was not added, to obtain anisoprene-acrylonitrile random copolymer.

The conversion ratio of isoprene and the conversion ratio ofacrylonitrile determined by gas chromatography were 92% and 82%,respectively. The weight average molecular weight (Mw), the numberaverage molecular weight (Mn), and the molecular weight distribution(Mw/Mn) of the isoprene-acrylonitrile random copolymer determined by GPC(with respect to a polystyrene standard sample) were 8,690, 6,980, and1.25, respectively.

It was found by ¹H-NMR analysis that the isoprene-acrylonitrile randomcopolymer included a terminal double bond in a ratio of 98%.

Example 8

A polymerization reaction was effected in the same manner as in Example5, except that dimethyl ditelluride and 1,1′-azobis(cyclohexane-1-carbonitrile) were not added, and thepolymerization reaction time was changed to 72 hours, to obtain anisoprene-acrylonitrile random copolymer.

The conversion ratio of isoprene and the conversion ratio ofacrylonitrile determined by gas chromatography were 75% and 63%,respectively.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of theisoprene-acrylonitrile random copolymer determined by GPC (with respectto a polystyrene standard sample) were 4,160, 3,080, and 1.35,respectively.

It was found by ¹H-NMR analysis that the isoprene-acrylonitrile randomcopolymer included a terminal double bond in a ratio of 97%.

Example 9

In a glovebox in which the internal atmosphere had been replaced bynitrogen, a 30 mL glass reaction vessel was charged with 2.56 g (20mmol) of n-butyl acrylate (manufactured by Wako Pure ChemicalIndustries, Ltd. (hereinafter the same)), 36.7 mg (0.20 mmol) of3-methyltellanyl-1-propene obtained in Example 1, 16.4 mg (0.10 mmol) ofazobisisobutyronitrile (manufactured by Wako Pure Chemical Industries,Ltd. (hereinafter the same)), and 0.24 g of mesitylene (internalstandard), and the mixture was stirred at 60° C. for 1 hour to effect apolymerization reaction.

The resulting polymerization reaction product was purified byevaporating a volatile component under reduced pressure, and thepurified product was dried to obtain an n-butyl acrylate polymer. Theconversion ratio of n-butyl acrylate determined by gas chromatographywas 91%.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of then-butyl acrylate polymer determined by GPC (with respect to apolystyrene standard sample) were 18,970, 15,240, and 1.25,respectively.

It was found by ¹H-NMR analysis that the n-butyl acrylate polymerincluded a terminal double bond in a ratio of 90%.

Example 10

In a glovebox in which the internal atmosphere had been replaced bynitrogen, a 30 mL glass reaction vessel was charged with 2.56 g (20mmol) of n-butyl acrylate, 36.7 mg (0.20 mmol) of3-methyltellanyl-1-propene obtained in Example 1, 16.4 mg (0.10 mmol) ofazobisisobutyronitrile, and 0.24 g of mesitylene (internal standard),and the mixture was stirred at 60° C. for 1 hour to effect apolymerization reaction. After the addition of 1.00 g (10 mmol) ofmethyl methacrylate (manufactured by Wako Pure

Chemical Industries, Ltd. (hereinafter the same)) and 28.5 mg (0.1 mmol)of dimethyl ditelluride obtained in Synthesis Example 1 to the reactionvessel, the mixture was stirred at 80° C. for 15 hours to effect apolymerization reaction.

The resulting polymerization reaction product was purified byevaporating a volatile component under reduced pressure, and thepurified product was dried to obtain an n-butyl acrylate-methylmethacrylate block copolymer. The conversion ratio of methylmethacrylate determined by gas chromatography was 100%.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of then-butyl acrylate-methyl methacrylate block copolymer determined by GPC(with respect to a polystyrene standard sample) were 50,900, 29,600, and1.71, respectively.

It was found by ¹H-NMR analysis that the n-butyl acrylate-methylmethacrylate block copolymer included a terminal double bond in a ratioof 88%.

Example 11

A polymerization reaction was effected in the same manner as in Example9, except that 2.08 g (20 mmol) of styrene (manufactured by TokyoChemical Industry Co., Ltd. (hereinafter the same)) was used instead ofn-butyl acrylate, to obtain a styrene polymer.

The conversion ratio of styrene determined by gas chromatography was91%. The weight average molecular weight (Mw), the number averagemolecular weight (Mn), and the molecular weight distribution (Mw/Mn) ofthe styrene polymer determined by GPC (with respect to a polystyrenestandard sample) were 10,860, 8,150, and 1.33, respectively.

It was found by ¹H-NMR analysis that the styrene polymer included aterminal double bond in a ratio of 97%.

Example 12

In a glovebox in which the internal atmosphere had been replaced bynitrogen, a 30 mL glass reaction vessel was charged with 2.08 g (20mmol) of styrene, 36.7 mg (0.20 mmol) of 3-methyltellanyl-1-propeneobtained in Example 1, 16.4 mg (0.10 mmol) of azobisisobutyronitrile,and 0.24 g of mesitylene (internal standard), and the mixture wasstirred at 60° C. for 1 hour to effect a polymerization reaction. Afterthe addition of 1.00 g (10 mmol) of methyl methacrylate and 28.5 mg (0.1mmol) of dimethyl ditelluride obtained in Synthesis Example 1 to thereaction vessel, the mixture was stirred at 80° C. for 15 hours toeffect a polymerization reaction.

The resulting polymerization reaction product was purified byevaporating a volatile component under reduced pressure, and thepurified product was dried to obtain a styrene-methyl methacrylate blockcopolymer.

The conversion ratio of methyl methacrylate determined by gaschromatography was 100%.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of thestyrene-methyl methacrylate block copolymer determined by GPC (withrespect to a polystyrene standard sample) were 26,600, 18,800, and 1.41,respectively.

It was found by ¹H-NMR analysis that the styrene-methyl methacrylateblock copolymer included a terminal double bond in a ratio of 92%.

Example 13

A polymerization reaction was effected in the same manner as in Example5, except that 1.00 g (10 mmol) of methyl methacrylate was used insteadof acrylonitrile, to obtain an isoprene-methyl methacrylate randomcopolymer. The conversion ratio of isoprene and the conversion ratio ofmethyl methacrylate determined by gas chromatography were 97% and 90%,respectively.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of theisoprene-methyl methacrylate random copolymer determined by GPC (withrespect to a polystyrene standard sample) were 9,110, 7,530, and 1.21,respectively.

It was found by ¹H-NMR analysis that the isoprene-methyl methacrylaterandom copolymer included a terminal double bond in a ratio of 96%.

Example 14

A polymerization reaction was effected in the same manner as in Example5, except that 1.28 g (10 mmol) of n-butyl acrylate was used instead ofacrylonitrile, to obtain an isoprene-n-butyl acrylate random copolymer.

The conversion ratio of isoprene and the conversion ratio of n-butylacrylate determined by gas chromatography were 99% and 87%,respectively.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of theisoprene-n-butyl acrylate random copolymer determined by GPC (withrespect to a polystyrene standard sample) were 5,800, 4,700, and 1.23,respectively.

It was found by ¹H-NMR analysis that the isoprene-n-butyl acrylaterandom copolymer included a terminal double bond in a ratio of 95%.

Example 15

A polymerization reaction was effected in the same manner as in Example5, except that 1.04 g (10 mmol) of styrene was used instead ofacrylonitrile, to obtain an isoprene-styrene random copolymer.

The conversion ratio of isoprene and the conversion ratio of styrenedetermined by gas chromatography were 93% and 73%, respectively.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of theisoprene-styrene random copolymer determined by GPC (with respect to apolystyrene standard sample) were 8,070, 6,580, and 1.19, respectively.

It was found by ¹H-NMR analysis that the isoprene-styrene randomcopolymer included a terminal double bond in a ratio of 98%.

Example 16

In a glovebox in which the internal atmosphere had been replaced bynitrogen, a 30 mL stainless steel autoclave was charged with 1.62 g (30mmol) of 1,3-butadiene (manufactured by Tokyo Chemical Industry Co.,Ltd.), 1.59 g (30 mmol) of acrylonitrile, 0.6 mg (0.003 mmol) of3-methyltellanyl-1-propene obtained in Example 1, 0.1 mg (0.0006 mmol)of dimethyl ditelluride, 1.5 mg (0.009 mmol) of1,1′-azobis(cyclohexane-1-carbonitrile), and 0.24 g of mesitylene(internal standard), and the mixture was stirred at 80° C. for 21 hoursto effect a polymerization reaction.

The resulting polymerization reaction product was purified byevaporating a volatile component under reduced pressure, and thepurified product was dried to obtain a butadiene-acrylonitrile randomcopolymer.

The conversion ratio of 1,3-butadiene and the conversion ratio ofacrylonitrile determined by gas chromatography were 81% and 58%,respectively.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of thebutadiene-acrylonitrile random copolymer determined by GPC (with respectto a polystyrene standard sample) were 332,300, 223,000, and 1.49,respectively.

It was found by ¹H-NMR analysis that the butadiene-acrylonitrile randomcopolymer included a terminal double bond in a ratio of 96%.

Example 17

In a glovebox in which the internal atmosphere had been replaced bynitrogen, a 30 mL glass reaction vessel was charged with 0.68 g (10mmol) of cis-1,3-pentadiene (manufactured by Tokyo Chemical IndustryCo., Ltd.), 0.53 g (10 mmol) of acrylonitrile, 1.2 mg (0.0067 mmol) of3-methyltellanyl-1-propene obtained in Example 1, 0.4 mg (0.0013 mmol)of dimethyl ditelluride, 0.8 mg (0.003 mmol) of1,1′-azobis(cyclohexane-1-carbonitrile), and 0.24 g of mesitylene(internal standard), and the mixture was stirred at 80° C. for 38 hoursto effect a polymerization reaction.

The resulting polymerization reaction product was purified byevaporating a volatile component under reduced pressure, and thepurified product was dried to obtain a cis-1,3-pentadiene-acrylonitrilerandom copolymer.

The conversion ratio of cis-1,3-pentadiene and the conversion ratio ofacrylonitrile determined by gas chromatography were 76% and 36%,respectively.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of thecis-1,3-pentadiene-acrylonitrile random copolymer determined by GPC(with respect to a polystyrene standard sample) were 89,400, 60,400, and1.48, respectively.

It was found by ¹H-NMR analysis that thecis-1,3-pentadiene-acrylonitrile random copolymer included a terminaldouble bond in a ratio of 92%.

Example 18

A polymerization reaction was effected in the same manner as in Example5, except that 49.1 mg (0.2 mmol) of 3-phenyltellanyl-1-propene obtainedin Example 2 was used instead of 3-methyltellanyl-1-propene, and 8.2 mg(0.02 mmol) of diphenyl ditelluride (manufactured by Aldrich) was usedinstead of dimethyl ditelluride, to obtain an isoprene-acrylonitrilerandom copolymer.

The conversion ratio of isoprene and the conversion ratio ofacrylonitrile determined by gas chromatography were 91% and 82%,respectively.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of theisoprene-acrylonitrile random copolymer determined by GPC (with respectto a polystyrene standard sample) were 5,740, 5,010, and 1.15,respectively.

It was found by ¹H-NMR analysis that the isoprene-acrylonitrile randomcopolymer included a terminal double bond in a ratio of 94%.

Example 19

A polymerization reaction was effected in the same manner as in Example5, except that 52.9 mg (0.2 mmol) of 3-[(n-butyl)tellanyl]-1-cyclohexeneobtained in Example 3 was used instead of 3-methyltellanyl-1-propene,and 7.5 mg (0.02 mmol) of dibutyl ditelluride obtained in SynthesisExample 2 was used instead of dimethyl ditelluride, to obtain anisoprene-acrylonitrile random copolymer.

The conversion ratio of isoprene and the conversion ratio ofacrylonitrile determined by gas chromatography were 91% and 84%,respectively. The weight average molecular weight (Mw), the numberaverage molecular weight (Mn), and the molecular weight distribution(Mw/Mn) of the isoprene-acrylonitrile random copolymer determined by GPC(with respect to a polystyrene standard sample) were 7,770, 6,150, and1.26, respectively.

It was found by ^(H)-NMR analysis that the isoprene-acrylonitrile randomcopolymer included a terminal double bond in a ratio of 99%.

Example 20

A polymerization reaction was effected in the same manner as in Example10, except that 48.3 mg (0.2 mmol) of methyl2-(methyltellanylmethyl)acrylate obtained in Example 4 was used insteadof 3-methyltellanyl-1-propene, to obtain an isoprene-acrylonitrilerandom copolymer.

The conversion ratio of isoprene and the conversion ratio ofacrylonitrile determined by gas chromatography were 86% and 76%,respectively.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of theisoprene-acrylonitrile random copolymer determined by GPC (with respectto a polystyrene standard sample) were 8,190, 5,570, and 1.47,respectively.

It was found by ¹H-NMR analysis that the isoprene-acrylonitrile randomcopolymer included a terminal double bond in a ratio of 85%.

Example 21

A polymerization reaction was effected in the same manner as in Example9, except that 3.14 g (20 mmol) of 2-(dimethylamino)ethyl methacrylatewas used instead of n-butyl acrylate, to obtain a 2-(dimethylamino)ethylmethacrylate polymer.

The conversion ratio of 2-(dimethylamino)ethyl methacrylate determinedby gas chromatography was 83%. The weight average molecular weight (Mw),the number average molecular weight (Mn), and the molecular weightdistribution (Mw/Mn) of the 2-(dimethylamino)ethyl methacrylate polymerdetermined by GPC (with respect to a polystyrene standard sample) were25,900, 19,300, and 1.34, respectively.

It was found by ¹H-NMR analysis that the 2-(dimethylamino)ethylmethacrylate polymer included a terminal double bond in a ratio of 87%.

Comparative Example 1

In a glovebox in which the internal atmosphere had been replaced bynitrogen, a 30 mL glass reaction vessel was charged with 28.7 mg (0.2mmol) of copper(I) bromide (manufactured by Wako Pure ChemicalIndustries, Ltd. (hereinafter the same)), 34.7 mg (0.2 mmol) ofN,N,N′,N″,N″-pentamethyldiethylenetriamine (manufactured by Wako PureChemical Industries, Ltd.), 0.68 g (10 mmol) of isoprene, 0.53 g (10mmol) of acrylonitrile, 24.2 mg (0.20 mmol) of allyl bromide, and 0.24 gof mesitylene (internal standard), and the mixture was stirred at 80° C.for 15 hours to effect a polymerization reaction.

The resulting polymerization reaction product was purified byevaporating a volatile component under reduced pressure, and thepurified product was dried. The conversion ratio of isoprene and theconversion ratio of acrylonitrile determined by gas chromatography were21% and 27%, respectively.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of theresulting product determined by GPC (with respect to a polystyrenestandard sample) were 370, 360, and 1.04, respectively. It was thusfound that an oligomer was obtained by the polymerization reaction.

Comparative Example 2

In a glovebox in which the internal atmosphere had been replaced bynitrogen, a 30 mL glass reaction vessel was charged with 28.7 mg (0.2mmol) of copper(I) bromide, 34.7 mg (0.2 mmol) ofN,N,N′,N″,N″-pentamethyldiethylenetriamine, 2 mL of toluene, 3.14 g (20mmol) of 2-(dimethylamino)ethyl methacrylate, 24.2 mg (0.20 mmol) ofallyl bromide, and 0.24 g of mesitylene (internal standard), and themixture was stirred at 80° C. for 15 hours to effect a polymerizationreaction.

The resulting polymerization reaction product was purified byevaporating a volatile component under reduced pressure, and thepurified product was dried to obtain a 2-(dimethylamino)ethylmethacrylate polymer.

The conversion ratio of 2-(dimethylamino)ethyl methacrylate determinedby gas chromatography was 42%.

The weight average molecular weight (Mw), the number average molecularweight (Mn), and the molecular weight distribution (Mw/Mn) of the2-(dimethylamino)ethyl methacrylate polymer determined by GPC (withrespect to a polystyrene standard sample) were 36,000, 13,300, and 2.71,respectively. Specifically, the 2-(dimethylamino)ethyl methacrylatepolymer had a relatively wide molecular weight distribution.

1. A method for producing a polymer comprising subjecting a radicallypolymerizable monomer to radical polymerization in a state in which aradical polymerization initiator is present in a polymerization system,wherein the radical polymerization initiator is an organotelluriumcompound represented by the following formula (1),

wherein R¹ represents a group selected from: an alkyl group having 1 to10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms which isunsubstituted, or substituted with a substituent selected from a halogenatom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and—CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms,a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxygroup having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8carbon atoms); an aryl group having 6 to 20 carbon atoms which isunsubstituted, or substituted with a substituent selected from a halogenatom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and—CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms,a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxygroup having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8carbon atoms); and an aromatic heterocyclic group which isunsubstituted, or substituted with a substituent selected from a halogenatom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and—CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms,a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxygroup having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8carbon atoms), each of R² and R³ independently represents a groupselected from: a hydrogen atom; an aliphatic hydrocarbon group having 1to 10 carbon atoms; an aryl group having 6 to 20 carbon atoms which isunsubstituted, or substituted with a substituent selected from a halogenatom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and—CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms,a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxygroup having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8carbon atoms); an aromatic heterocyclic group which is unsubstituted, orsubstituted with a substituent selected from a halogen atom, an alkylgroup having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbonatoms, an amino group, a nitro group, a cyano group, and —CORa (whereinRa represents an alkyl group having 1 to 8 carbon atoms, a cycloalkylgroup having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbonatoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy grouphaving 6 to 10 carbon atoms or a haloalkyl group having 1 to 8 carbonatoms); a halogen atom; a carboxyl group; a hydrocarbyl oxycarbonylgroup having 2 to 10 carbon atoms; a cyano group; and an amide group,and each of R⁴, R⁵ and R⁶ independently represents a group selectedfrom: a hydrogen atom; an aliphatic hydrocarbon group having 1 to 10carbon atoms; an aryl group having 6 to 20 carbon atoms which isunsubstituted, or substituted with a substituent selected from a halogenatom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and—CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms,a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxygroup having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8carbon atoms); an aromatic heterocyclic group which is unsubstituted, orsubstituted with a substituent selected from a halogen atom, an alkylgroup having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbonatoms, an amino group, a nitro group, a cyano group, and —CORa (whereinRa represents an alkyl group having 1 to 8 carbon atoms, a cycloalkylgroup having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbonatoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy grouphaving 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbonatoms); a halogen atom; a carboxyl group; a hydrocarbyl oxycarbonylgroup having 2 to 10 carbon atoms; a cyano group; and an amide group,and a group represented by the following formula (2), wherein 2 groupsselected from R² to R⁶ may bond together to form a ring other than anaromatic ring,

wherein R⁷ represents a group selected from: an alkyl group having 1 to10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms which isunsubstituted, or substituted with a substituent selected from a halogenatom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and—CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms,a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxygroup having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8carbon atoms); an aryl group having 6 to 20 carbon atoms which isunsubstituted, or substituted with a substituent selected from a halogenatom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and—CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms,a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxygroup having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8carbon atoms); and an aromatic heterocyclic group which isunsubstituted, or substituted with a substituent selected from a halogenatom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and—CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms,a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxygroup having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8carbon atoms), and each of R⁸ and R⁹ independently represents a groupselected from: a hydrogen atom; an aliphatic hydrocarbon group having 1to 10 carbon atoms; an aryl group having 6 to 20 carbon atoms which isunsubstituted, or substituted with a substituent selected from a halogenatom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and—CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms,a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxygroup having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8carbon atoms); an aromatic heterocyclic group which is unsubstituted, orsubstituted with a substituent selected from a halogen atom, an alkylgroup having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbonatoms, an amino group, a nitro group, a cyano group, and —CORa (whereinRa represents an alkyl group having 1 to 8 carbon atoms, a cycloalkylgroup having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbonatoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy grouphaving 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbonatoms); a halogen atom; a carboxyl group; a hydrocarbyl oxycarbonylgroup having 2 to 10 carbon atoms; a cyano group; and an amide group,wherein the wavy line represents a bond with the carbon atomsconstituting the double bond in formula (1), wherein one of the terminalof the polymer produced is a group represented by(R⁵)(R⁶)C═C(R⁴)—C(R²)(R³)- that is derived from the organotelluriumcompound.
 2. The method for producing a polymer according to claim 1,wherein the radically polymerizable monomer is subjected to radicalpolymerization in a state in which an azo-based radical generator isfurther present in the polymerization system.
 3. The method forproducing a polymer according to claim 1, wherein the radicallypolymerizable monomer is subjected to radical polymerization in a statein which light is applied to the polymerization system.
 4. The methodfor producing a polymer according to claim 1, wherein the radicallypolymerizable monomer is subjected to radical polymerization in a statein which a ditelluride compound represented by a formula (3) is furtherpresent in the polymerization system,R¹⁰Te-TeR¹¹   (3) wherein each of le and independently represents agroup selected from an alkyl group, a substituted or unsubstitutedcycloalkyl group, a substituted or unsubstituted aryl group, and asubstituted or unsubstituted heteroaromatic ring group.
 5. The methodfor producing a polymer according to claim 1, wherein the molecularweight distribution of the polymer produced is 1.01 to 2.50.